Microbicidal agents based on quinolonecarboxylic acid

Abstract

Combating microorganisms, particularly in agriculture, with a 1-cyclopropyl-1,4-dihydro-4-oxo-quinolinecarboxylic acid of the formula <IMAGE> in which R1 is hydrogen, fluorine, chlorine, bromine or nitro, R2 is hydrogen, chlorine, fluorine or the group <IMAGE> particularly a 4-piperazinyl radical, or an acid addition, alkali metal, alkaline earth metal or heavy metal salt thereof which is tolerated by plants, or a hydrate thereof. Some of the compounds are known.

We claim: 
     
       1. A method of combating a plant fungus on plants or parts thereof which comprises applying to the fungus an effective amount for combating said fungus of a 1-cyclopropyl-1,4-dihydro-4-oxo-quinolinecarboxylic acid of the formula ##STR121## in which R 1  is hydrogen, fluorine, chlorine, bromine or nitro, R 2  is hydrogen, chlorine, fluorine or the group ##STR122## R 3  and R 4  each independently is alkyl or hydroxyalkyl which has 1 to 4 carbon atoms, or   R 3  and R 4 , together with the nitrogen atom on which they are positioned, form a 5-membered or 6-membered saturated or partially unsaturated heterocyclic ring which can optionally contain in its ring oxygen, sulphur or an SO, SO 2  or NR 5  group and which is optionally substituted by at least one member selected from the group consisting of alkyl with 1 to 6 carbon atoms, alkenyl with 2 to 6 carbon atoms, phenyl and hydroxyl,   R 5  is hydrogen, alkyl which has 1 to 12 carbon atoms and is optionally substituted by hydroxyl and alkoxy with 1 to 4 carbon atoms, or is phenylalkyl which has 1 to 3 carbon atoms in the alkyl part and is optionally substituted by nitro, amino or the group --O--CH 2  --O--, or is phenyl which is optionally substituted by at least one member selected from the group consisting of halogen, halogenoalkyl with 1 or 2 carbon atoms and with up to 5 halogen atoms, hydroxy, alkoxy with 1 to 3 carbon atoms, the group --O--CH 2  --O--, pyridyl, pyrimidinyl and the grouping ##STR123## A is an optionally substituted alkylene chain with 1 to 4 carbon atoms, R 6  is hydrogen, alkyl with 1 to 6 carbon atoms, or phenyl which is optionally substituted by at least one member selected from the group consisting of hydroxyl, methoxy and halogen,   X is oxygen or the groupings ═NOR', ═N--NH--R" or (OR"') 2 ,   R' is hydrogen, alkyl with 1 to 6 carbon atoms, cycloalkyl with 5 or 6 carbon atoms, benzyl, chlorobenzyl or tetrahydropyranyl,   R" is methyl, phenyl, carbamoyl or thiocarbamoyl, and   R"' is methyl or ethyl, or   (OR"') 2  represents ##STR124## or an acid addition, alkali metal, alkaline earth metal or heavy metal salt thereof which is tolerated by plants, or a hydrate thereof.   
     
     
       2. The method according to claim 1, in which   R 1  is hydrogen, fluorine, chlorine or nitro,   R 2  is chlorine, fluorine or the group ##STR125## R 3  and R 4  each independently is alkyl with 1 to 3 carbon atoms or alkyl which has 2 or 3 carbon atoms and is monosubstituted by hydroxy, or   R 3  and R 4 , together with the nitrogen atom on which they are positioned, are pyrrolidinyl, piperidine, tetrahydropyridyl, morpholinyl, thiomorpholinyl, 1,1-dioxo-4-thiomorpholinyl or R 5  -piperazinyl, each of which is optionally mono-, di- or tri-substituted by at least one member selected from the group consisting of alkyl with 1 to 4 carbon atoms, phenyl and hydroxyl,   R 5  is hydrogen, alkyl with 1 to 12 carbon atoms, alkyl which has 1 to 4 carbon atoms and is monosubstituted by hydroxyl, alkyl which has 1 to 4 carbon atoms and is monosubstituted by methoxy, phenyl which is optionally mono-, di- or tri-substituted by hydroxyl, alkoxy with 1 or 2 carbon atoms, trifluoromethyl, fluorine or dioxymethylene, pyridyl, pyrimidinyl, phenalkyl which has 1 or 2 carbon atoms in the alkyl part and is optionally substituted by dioxymethylene, or the grouping ##STR126## A is an alkylene chain with 1 to 3 carbon atoms, R 6  is hydrogen, alkyl with 1 to 4 carbon atoms, or phenyl which is optionally mono-, di, or tri-substituted by at least one of hydroxyl, fluorine, chlorine or methoxy,   X is oxygen or the grouping ═NOR', ═N--NHR" or (OR"') 2 ,   R' is alkyl with 1 to 3 carbon atoms, benzyl or tetrahydropyranyl,   R" is methyl, ethyl, carbamoyl or thiocarbamoyl, and   R"' methyl, or   (OR"') 2  is ##STR127##   
     
     
       3. The method according to claim 1, wherein such compound is 1-cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-7-(4-methyl-1-piperazinyl)-3-quinolinecarboxylic acid of the formula ##STR128## or an acid addition, alkali metal, alkaline earth metal or heavy metal salt thereof which is tolerated by plants, or a hydrate thereof. 
     
     
       4. The method according to claim 1, wherein such compound is 1-cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinolinecarboxylic acid of the formula ##STR129## or an acid addition, alkali metal, alkaline earth metal or heavy metal salt thereof which is tolerated by plants, or a hydrate thereof. 
     
     
       5. The method according to claim 1, wherein such compound is 1-cyclopropyl-6-fluoro-7-(4-ethyl-1-piperazinyl)-1,4-dihydro-4-oxo-3-quinolinecarboxylic acid of the formula ##STR130## or an acid addition, alkali metal, alkaline earth metal or heavy metal salt thereof which is tolerated by plants, or a hydrate thereof. 
     
     
       6. The method according to claim 1, wherein such compound is 1-cyclopropyl-6-fluoro-7-(4-isopropyl-1-piperazinyl)-1,4-dihydro-4-oxo-3-quinolinecarboxylic acid of the formula ##STR131## or an acid addition, alkali metal, alkaline earth metal or heavy metal salt thereof which is tolerated by plants, or a hydrate thereof.